We present an investigation into the use of an explicitly correlated plane wave basis for periodic wavefunction expansions at the level of second-order Møller-Plesset (MP2) perturbation theory. The convergence of the electronic correlation energy with respect to the one-electron basis set is investigated and compared to conventional MP2 theory in a finite homogeneous electron gas model. In addition to the widely used Slater-type geminal correlation factor, we also derive and investigate a novel correlation factor that we term Yukawa-Coulomb. The Yukawa-Coulomb correlation factor is motivated by analytic results for two electrons in a box and allows for a further improved convergence of the correlation energies with respect to the employed basis set. We find the combination of the infinitely delocalized plane waves and local short-ranged geminals provides a complementary, and rapidly convergent basis for the description of periodic wavefunctions. We hope that this approach will expand the scope of discrete wavefunction expansions in periodic systems.
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28 August 2013
Research Article|
August 29 2013
Explicitly correlated plane waves: Accelerating convergence in periodic wavefunction expansions
Andreas Grüneis;
Andreas Grüneis
a)
1Chemistry Department,
University of Cambridge
, Lensfield Road, Cambridge CB2 1EQ, United Kingdom
2Faculty of Physics and Center for Computational Materials Science,
University Vienna
, Sensengasse 8/12, A-1090 Vienna, Austria
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James J. Shepherd;
James J. Shepherd
1Chemistry Department,
University of Cambridge
, Lensfield Road, Cambridge CB2 1EQ, United Kingdom
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Ali Alavi;
Ali Alavi
1Chemistry Department,
University of Cambridge
, Lensfield Road, Cambridge CB2 1EQ, United Kingdom
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David P. Tew;
David P. Tew
3School of Chemistry,
University of Bristol
, Bristol BS8 1TS, United Kingdom
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George H. Booth
George H. Booth
b)
1Chemistry Department,
University of Cambridge
, Lensfield Road, Cambridge CB2 1EQ, United Kingdom
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a)
Electronic mail: andreas.grueneis@univie.ac.at
b)
Electronic mail: ghb24@cam.ac.uk
J. Chem. Phys. 139, 084112 (2013)
Article history
Received:
June 27 2013
Accepted:
August 05 2013
Citation
Andreas Grüneis, James J. Shepherd, Ali Alavi, David P. Tew, George H. Booth; Explicitly correlated plane waves: Accelerating convergence in periodic wavefunction expansions. J. Chem. Phys. 28 August 2013; 139 (8): 084112. https://doi.org/10.1063/1.4818753
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